EP2734600B1 - Aluminumsulfonatsalz zur kontrollierten tensidfreigabe bei einem öl-gewinnungsverfahren - Google Patents

Aluminumsulfonatsalz zur kontrollierten tensidfreigabe bei einem öl-gewinnungsverfahren Download PDF

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Publication number
EP2734600B1
EP2734600B1 EP12737670.5A EP12737670A EP2734600B1 EP 2734600 B1 EP2734600 B1 EP 2734600B1 EP 12737670 A EP12737670 A EP 12737670A EP 2734600 B1 EP2734600 B1 EP 2734600B1
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Prior art keywords
salt
surfactant
weight percent
surfactants
alkyl sulfonate
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EP12737670.5A
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English (en)
French (fr)
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EP2734600A1 (de
Inventor
Yun Chea Chang
Mazen KANJ
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Saudi Arabian Oil Co
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Saudi Arabian Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids

Definitions

  • the invention is new compositions, delivery systems, and methods suitable for the enhanced oil recovery process.
  • Surfactants are used in the enhanced oil recovery process.
  • the presence of surfactant at water and oil interface facilitates oil recovery. It would be ideal to have a sustained and constant concentration at the interface.
  • Surfactants and other chemicals are often mixed with water and driven into the reservoir in the enhanced oil recovery (EOR) process.
  • Surfactant molecules especially anionic surfactants, adsorb to the rock before they interact with oil. Adsorption of the surfactant results in the loss of effective amount of surfactant for mobilizing the oil. The adsorption problem worsens when anionic surfactants encounter carbonate rocks that are Lewis acid in nature.
  • surfactants precipitate with cations from the rock and from the saline water. In either case, some surfactants are lost before they have a chance to solubilize oil.
  • the exact amount of surfactant adsorption depends on the type of rock, pore surface area, water salinity and the type of surfactants. In general, roughly one milligram of surfactant may adsorb to one gram of rock.
  • compositions comprising salts of lignin sulfonate and hydroxy-aluminium sulfonate and water for stabilizing soil formations from the effects of water and increasing the resistance of paper products.
  • compositions for the controlled release of surfactants in oil recovery operation being made of an aqueous sulfonate solution; an anionic surfactant; and a salt selected from aluminium nitrate nanohydrate, calcium chloride dihydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts, wherein the mean diameter of the salt particles is between 20 nm and 100 nm and salt solubility of the composition is less than 100 ppm at room temperature.
  • the composition may additionally contain hydrolyzed polyacrilamide.
  • a hydrocarbon recovery composition comprising a composition which comprises an aqueous sulfonate solution; an anionic surfactant; and a salt selected from aluminium nitrate nanohydrate, calcium chloride dihydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts, wherein the mean diameter of the salt particles is between 20 nm and 100 nm and salt solubility of the composition is less than 100 ppm at room temperature.
  • the composition may additionally contain hydrolyzed polyacrilamide.
  • a delivery system for controlling the release of surfactants in hydrocarbon recovery operation, the delivery system comprising an aqueous sulfonate solution; an anionic surfactant; and a salt selected from aluminium nitrate nanohydrate, calcium chloride dihydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts, wherein the mean diameter of the salt particles is between 20 nm and 100 nm and salt solubility of the delivery system is less than 100 ppm at room temperature; in an amount operable such that the surfactant reduces surface tension of the hydrocarbon so that oil recovery is increased.
  • the delivery system may further contain hydrolyzed polyacrilamide.
  • Also described is a method of delivering a controlled release of surfactants composition including the following the steps, such as: (1) delivering a solution into a reservoir, the solution that contains an aqueous sulfonate solution; an anionic surfactant; and a salt selected from aluminium nitrate nanohydrate, calcium chloride dihydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts; wherein the mean diameter of the salt particles is between 20 nm and 100 nm and salt solubility of the delivery solution is less than 100 ppm at room temperature; and (2) delivering water to the reservoir.
  • a method of treating a hydrocarbon containing formation by (a) providing a hydrocarbon recovery composition to at least a portion of the hydrocarbon containing formation, wherein the hydrocarbon recovery composition comprises (1) an aqueous sulfonate solution; (2) an anionic surfactant; and (3) a salt selected from aluminium nitrate nanohydrate, calcium chloride dihydrate, magnesium chloride hexahydrate, cobalt chloride hexahydrate, and other metal salts; wherein the mean diameter of the salt particles is between 20 nm and 100 nm and salt solubility of the hydrocarbon recovery composition is less than 100 ppm at room temperature; and (b) allowing the hydrocarbon recovery composition to interact with hydrocarbons in the hydrocarbon containing formation.
  • Embodiments of the present invention provide a way to slow release surfactant molecules, maintain the concentration at constant levels, and sustain the release over a long period of time.
  • the rock in the reservoir is porous with wide pore size distribution.
  • the pore can be as small as 1 micron and as big as 20 micron. Larger size particles may be trapped by the pores.
  • surfactant salt particles to be small such that they can traverse through the pores.
  • the salt particles should also be big enough that they contain sufficient amount of surfactant for sustained release. We figure that 50 - 200 nm would be an ideal size.
  • the surfactant salt solubility is 100 ppm and 1.0 weight percent of which is added in 1 liter of solution, then the surfactant concentration that is released by the surfactant salt is held constant at 100 ppm.
  • the solution in which the surfactant salt is dispersed in can range from de-ionized water to saline water, with salinity as high as 25 weight percent. If the soluble surfactant is consumed upon contacting oil within one day, then another 100 ppm of surfactant can be replenished by the surfactant salt. The replenishing process is driven by the thermodynamic equilibrium between the solid salt and soluble surfactant. In other words, 100 ppm of free surfactant concentration will be maintained in the solution automatically in the presence of surfactant salt particles. The amount of surfactant salt would last a total of 10 days, regardless of the size of particles or capsules.
  • an aqueous dispersion according to claim 1 is injected into the oil-containing reservoir.
  • the surfactant quickly deposits and, depending on the amount used, may be saturated on the oil-water interface.
  • the oil thus solubilized by the surfactant, can be recovered.
  • residual oil that lies behind the initial oil-water interface has less a chance of interacting with the surfactant and may remain immobilized.
  • Sulfonate surfactant may form salts with cations.
  • the salt formation is often considered problematic during enhanced oil recover (EOR) since it results in the loss of surfactants.
  • EOR enhanced oil recover
  • the salt can be engineered in such ways that it benefits the EOR process.
  • the surfactant salts or capsules have to be as small as 200 nm or less such that they can travel through the pore in the reservoir.
  • Particle size can be manipulated by controlling the nucleation rate in the precipitation of surfactant salts.
  • Another way to manipulate the particle size is to use the mechanical milling device.
  • these nano-particles have to be dispersible in the reservoir environment; i.e. up to 100° C and 25 wt% salinity.
  • active ingredients are often delivered in a controlled release fashion.
  • concentration of active ingredients is maintained at the targeted area.
  • One dosage of active ingredients can sustain the efficacy in a longer period of time.
  • surfactants will be delivered and released at oil and water interface.
  • the delivered surfactant capsules or particles are akin to micro reservoirs that feed surfactant molecules to the oil/water interface at a constant concentration and a constant rate. As a result, residual oil may be solubilized continuously.
  • anionic surfactants such as sulfonates
  • the sulfonated surfactant has a negative charge which reacts with positively charge cat ions.
  • some resulting salts are partially or sparingly water soluble.
  • the salts have limited solubility in water and thereby the surfactant salts serve as reservoirs for surfactant molecules.
  • Anionic surfactant salts precipitated by different cations have different solubility, which affects final particle size and amount of free surfactant in solution.
  • free surfactant concentration can be regulated by the choice of surfactant salts.
  • surfactant salt particles can be made smaller than 200 nm, smaller than 100 nm, and even smaller than 50 nm.
  • surfactant adsorption depends on the concentration of free surfactants
  • the surfactant salt particles limit the amount of free surfactant concentration and thereby mitigate adsorption.
  • the invention method supplies a constant flux of surfactant molecules from nano particles of surfactant salt. Because of this sustained supply of fresh surfactant molecules, more residual oil may be recovered.
  • the invention provides colloidal surfactant salts that maintain a constant free surfactant concentration in the solution. Because of this constant and sustained supply of fresh surfactant molecules more residual oil may be recovered.
  • a slug of the aqueous dispersion according to claim 1 (containing nano particles of surfactant salts, polymer and water) is injected into the reservoir. After a shut-in period of from 1 to 1000 hours, the slug is followed by a water flood. The rate of flood may be adjusted such that optimum amount of oil is recovered.
  • a metal salt is selected from aluminum nitrate nanohydrate, calcium chloride dihydrate, magnesium chloride hexahydrate, and cobalt chloride hexahydrate.
  • the metal salt is selected from aluminum nitrate nanohydrate, calcium chloride dihydrate, magnesium chloride hexahydrate, and cobalt chloride hexahydrate.
  • To the polymer/salt mixture between 0.05 to 5 weight percent of alkyl sulfonate is then added with vigorous stirring at temperatures between 0°C and 90°C.
  • the particle size is measured by Zetasizer, such as for example and without limitation, one made by Malvern Instrument, and number averaged particle size is determined.
  • between 0.05 and 5 weight percent of a metal salt at temperatures between 0°C and about 90°C is added to between 0.05 to 5 weight percent of alkyl sulfonate with vigorous stirring.
  • the resulting salt dispersion is centrifuged and filtered.
  • the supernatant sulfonate concentration in the supernatant is measured by the Total Carbon Analyzer.
  • an aqueous dispersion consisting of 0.05 to 5 weight percent of partially hydrolyzed polyacrylamide, and 0.05 to 5 weight percent of anionic surfactant salt particles with mean particle size less than 200 nm, is injected into oil-containing reservoir.
  • the anionic surfactant salt particles are selected from aluminium alkyl sulfonate, calcium alkyl sulfonate, magnesium alkyl sulfonate, and cobalt alkyl sulfonate.
  • the injected dispersion is then kept in the reservoir for 1 hour to 1,000 hours. After the shut in period, the dispersion slug is followed by water flooding.
  • This example demonstrates that small particle size aluminum sulfonate salt can be prepared.
  • Two ml of 0.3% partially hydrolyzed polyacrylamide was mixed with two ml of 1% aluminum nitrate nonahydrate at 0° C.
  • Nineteen ml of 0.1 wt % (1000 ppm) alkyl sulfonate (trade name MLA-0371, obtained from Chemtura) was then added with vigorous stirring.
  • the resulting precipitates particle size was measured by Zetasizer (Malvern Instrument) and number averaged particle size was determined to be 109 nm.
  • This example demonstrates that small particle size calcium sulfonate salt can be prepared.
  • This example is similar to Example 1 , except that 1% calcium chloride dihydrate was used instead of aluminum nitrate nonahydrate. The resulting particle size was 73 nm.
  • This example demonstrates that small particle size magnesium sulfonate salt can be prepared.
  • This example is similar to Example 1 , except that 1% magnesium chloride hexahydrate was used instead of aluminum nitrate nonahydrate. The resulting particle size was 62 nm.
  • This example demonstrates that small particle size cobalt sulfonate salt can be prepared.
  • This example is similar to Example 1 , except that 1% cobalt chloride hexahydrate was used instead of aluminum nitrate nonahydrate. The resulting particle size was 87 nm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 1 , except that no partially hydrolyzed polyacrylamide solution was added. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 6.3 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was controlled to a constant concentration of 63 ppm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 5, except that calcium chloride dihydrate, instead of aluminum nitrate nonahydrate, was used. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 8.3 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was controlled to a constant concentration of 83 ppm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 5, except that magnesium chloride hexahydrate, instead of aluminum nitrate nonahydrate, was used. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 30 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was controlled to a constant concentration of 300 ppm.
  • This example demonstrates that the free sulfonate concentration in the supernatant can be modulated by the presence of sulfonate salt.
  • This example is similar to Example 5, except that cobalt chloride hexahydrate, instead of aluminum nitrate nonahydrate, was used. The resulting salt dispersion was centrifuged and filtered. The supernatant sulfonate concentration in the supernatant was measured by the Total Carbon Analyzer. It was found that the supernatant contained 10.6 parts per million of sulfonate. In other words, initial surfactant concentration of 1,000 ppm was controlled to a constant concentration of 106 ppm.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Water Treatment By Sorption (AREA)
  • Lubricants (AREA)

Claims (3)

  1. Wässrige Dispersion zur kontrollierten Freigabe anionischer Tenside bei einer Kohlenwasserstoffgewinnungsarbeit, bestehend aus:
    0,05 bis 5 Gewichtsprozent teilweise hydrolysiertem Polyacrylamid; und
    0,05 bis 5 Gewichtsprozent Salzteilchen von anionischem Tensid mit einer mittleren Teilchengröße von weniger als 200 nm,
    wobei die Salzteilchen von anionischem Tensid unter Aluminiumalkylsulfonat, Calciumalkylsulfonat, Magnesiumalkylsulfonat und Kobaltalkylsulfonat ausgewählt werden und wobei die Teilchen in einer Reservoirumgebung von bis zu 100 °C und einer Salinität von 20 Gew.-% dispergierbar sind.
  2. Verfahren für die Herstellung einer wässrigen Dispersion nach Anspruch 1 zur kontrollierten Freigabe anionischer Tenside bei einer Kohlenwasserstoffgewinnungsarbeit, wobei das Verfahren Folgendes umfasst:
    a) Herstellen einer wässrigen Mischung von Polymer/Salz durch Mischen von 0,1 bis 2,0 Gewichtsprozent teilweise hydrolysiertem Polyacrylamid mit 0,05 bis 5 Gewichtsprozent eines Metallsalzes bei einer Temperatur zwischen 0 °C und 120 °C; und Zugeben zu der Mischung von Polymer/Salz von 0,05 bis 5 Gewichtsprozent anionischem Tensid unter kräftigem Rühren bei einer Temperatur zwischen 0 °C und 90 °C, wobei das Metallsalz aus der Gruppe ausgewählt wird bestehend aus Aluminiumnitratnonahydrat, Calciumchloriddihydrat, Magnesiumchloridhexahydrat und Kobaltchloridhexahydrat und das anionische Tensid Alkylsulfonat ist; und
    wobei die resultierenden anionischen Tensidsalzpräzipitate eine mittlere Teilchengröße von weniger als 200 nm aufweisen und in einer Reservoirumgebung von bis zu 100 °C und einer Salinität von 25 Gew.-% dispergierbar sind.
  3. Verfahren zum Behandeln einer Kohlenwasserstoff enthaltenden Formation, wobei das Verfahren aus Folgendem besteht:
    (a) Injizieren einer wässrigen Dispersion nach Anspruch 1 in ein ölhaltiges Reservoir; und
    (b) Halten der injizierten Dispersion in dem Reservoir für eine Einschlusszeitspanne von 1 Stunde bis 1000 Stunden; und
    (c) nach der Einschlusszeitspanne erfolgendes Befluten mit Wasser.
EP12737670.5A 2011-07-18 2012-07-10 Aluminumsulfonatsalz zur kontrollierten tensidfreigabe bei einem öl-gewinnungsverfahren Active EP2734600B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/184,974 US8946132B2 (en) 2011-07-18 2011-07-18 Controlled release of surfactants for enhanced oil recovery
PCT/US2012/046034 WO2013012607A1 (en) 2011-07-18 2012-07-10 Aluminum sulphonate salt for controlled release of surfactants in an enhanced oil recovery process

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EP2734600A1 EP2734600A1 (de) 2014-05-28
EP2734600B1 true EP2734600B1 (de) 2019-11-13

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US (1) US8946132B2 (de)
EP (1) EP2734600B1 (de)
JP (1) JP5864740B2 (de)
CN (1) CN103748189B (de)
CA (1) CA2840991C (de)
WO (1) WO2013012607A1 (de)

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CA2840991A1 (en) 2013-01-24
CN103748189B (zh) 2018-04-20
CN103748189A (zh) 2014-04-23
JP2014523951A (ja) 2014-09-18
EP2734600A1 (de) 2014-05-28
CA2840991C (en) 2016-01-26
JP5864740B2 (ja) 2016-02-17
WO2013012607A1 (en) 2013-01-24
US20130023450A1 (en) 2013-01-24
US8946132B2 (en) 2015-02-03

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